Production of color photographic images



, acety'l-p-naphthylamine,

Patented May 22 1945 UNITED STATESIHPATENT OFFICE v 2,376,579 PRODUCTIONOF ooLon PHOTOGRAPHIC IMAGES I Alfred Friihlich and Wilhelm Schneider,Dessau,

Germany, assignors to General Aniline & Film Corporation, Delaware NewYork, N. Y., a corporation of Application February 17, 1942, Serial No.431,27

) In Germany October 18, 1940 12 Claims.

images by color forming development it is known to use arylides ofa-p-ketocarboxylic acids as dyefo'rmers are added to the developingsolution or, if they are sufiiciently fast to diffusion, to the silverhalide emulsion layers during the preparation thereof. Thea-fl-ketocarboxylic acids include, for instance, the followingcompounds:

' acetoacetyl p-chloraniline, acetoacetylanisidine,

acetoacetoacetyl-o-chloraniline; benzoylacetyl-fi-naphthylainine,benzoylacetyl-p-chloraniline, dodecylacetic acid anilide,'stearylacetylanthranilic acid, furfuroyl-p-chlop anilide,benzoylacetylZ-aminobenzthiazole. For the production of colorphotographic images by acetoacetyl-o-chloro-m-methoxyan iline,

layers containing non-difiusing dyestufiformers it is of especialimportance to adjust the color tones of the single partial dyestufiimages so that they fulfil the theoretical requirements of the tricolorprocess as completely as possible; The

' dyestuffs produced with such dyestuif formers must therefore exhibitq'uit'e'particular spectral properties in order that an optimum of thecolor reproduction is reached. -Itis, for instance, necessary that ondevelopment the dyestuif formers f for the yellow yield dyestufis theabsorption maximum of which is as far as possible in the shortwaveregion of the spectrum and the absorption range of which is inclinedtowards the long-wave stuff formers for the yellow image. The dyestufimeans of'multi-layer materials with emulsion" to the amide group, theseaminoigroups aving linked thereto radicals producing fastnes -todiffusion, if required. The dyestuff formers of the invention producedyestuffs which'exhibit an absorption maximum below 450 m, a very steepdescent of the absorption curve towards the longwave region and a. veryfavorable solubility in diluted alkalies. The absorptive powers areshown in the drawing in which I is the absorption curve of the dyestufiformed from; l-acetoacetylamino 4 methyloctadecylaminobenzene-3-sulfonic acid and p dimethylaminoaniline and 2 is the absorption curveof the dyestufi produced from the known dyestufi componentacetoacetylaniline and the developing substance.

Dyestuff formers of the present invention are, for instance, thefollowing compounds: l-acetoacetylamino -,4 methyloctadecylaminobenzene-3-sulfonic acid, 1-acetoacetylamino-4-methyloctadecylaminonaphthalene 3sulfonic acid, 1 acetoacetylamino 2methyloctadecylaminobenzene-5-sulfonic acid, l-acetoacetylamino-4-octadecylaminobenzene-3-sulfonic acid, l-acetoacetylamino-4perhydrodiphenylaminobenzene 3-sulfonic acid,1-acetoacetylamind-4-abietinylaminobenzene-3-sulfonic acid,v1-stearylacety1-- amino-4-methylcyclohexylaminobenzene-3 car I vboxylicacid, 1-benzoylacetylamino-2-methyloctadecyl aminobenzene-5-carboxylicacid, the nucleus of the benzoyl radical of which, may carry anysubstituents, .1 2.6-di-(acetoacetylamino)--1-methyloctadecylaminobenzene 4 sulfonic acid,

2.5 di-(acetoacetylamino) 1 methyloctadecylaminobenzenel-sulfonic acid,and l-acetoacetylamino-4-sulfooleylaminobenzene.

1 The dyestufi formers are prepared in known .manner by reacting thecorreseponding nitrochlorobenzenecarboxylic acids or -sulfonic acids inknown manner.

vide new dyestufi: formers for the yellow which correspond with theserequirements as complete- H ly as possible. I Further objects willappear more in detail hereinafter. Reference is made to the accompanyingdrawing in which an absorption curve of a dyestuffformed from a.dyestuff com.- ponent of the present invention i compared with anabsorption curve of a dyestufi derived from a known component. Theobjects of the'invention are accomplished by using as the dyestuffcomponent for-the yellow aromatic acylacetic 'acid amides which carry atleast one group capable of'rendering the compo- I nent water-soluble andone or several secondary or tertiary amino groups in the ring systemlinked The dyestufi formers of the invention are especially easilysoluble, for instance, as alkali metal salts and the solution can beincorporated into the silver halide emulsion before casting. Thesecondary or tertiary amino groups may carry 1 various radicalspreventing di'ifusion as, for instance, disclosed in U. S.Patents'2,186,852, 2,186,- 851,; 2,186,733, 2,186,732, 2,186,734,-2,186,719,

2,186,847 dated January 9,1940, .U. s. Patents 2,179,238, 2,17 9,244,2,178,612 dated November 7, 1939, and U. S. Patents 2,280,722,2,292,575, 2,307,

' 399 and 2,303,928, Italian Patents 344,648, 344,649,

French Patent 844,637, and U. S. Patent applications Ser. Nos. 284,258filed July 13, 1939, 333,814 filed May 7, 1940, 335,144 filed May 14,1940,

341,180 filed June 18, 1940, and 362,592 filed October 24, 1940. Inparticular the secondary and ,a tertiary amino groups may contain one orseveral straight or branched carbon chains as substituicals and R1 is analiphatic hydrocarbon radical,

said'water-solubilizing group being attached to a carbon atom selectedfrom the group consisting of a nuclear carbon atom of said ring systemand a carbon atom of said long-chain aliphatic hydrocarbon radical, anddeveloping said emulsion with an aromatic primary amino developer.

2. The process as defined in claim 1 wherein the substituents on thenitrogen atom of said layers on one or both sides of a support and, if

necessary, filter layers, intermediate layers or anti-halation layers.The color images may be produced by simple or reversal development asnegatives or positives, respectively.

For the production of color images 3 g. of the dyestuff former aredissolved in a mixture of 100 cc. of water and 8 cc. of n/ 1 sodiumhydroxide solution. The obtained solution is then added to 300 cc. of asilver halide gelatin emulsion whereupon the emulsion is usually cast toform alayer and dried. The exposed layer is treated with a color formingdeveloper as, for instance, p-di- 'methylaminoaniline. After removingthe addi-,

tionally formed silver image by means of Farmers reducer (potassiumferricyanide solution) one obtains a yellow dyestufi image.

Instead of the sodium salt other soluble salts of the dyestufi formermay be used, for instance other alkali metal salts. Groups making thedyestufi former soluble in water are, for instance, sulfo, carboxyl andhydroxyl. I

Further dy'estufi formers according to the present invention are, forinstance, the following compounds:

/C1a s1 CH:.CO.CH:.CO.NH N\ CH3 S0311 s u CH; CO CHg.CO.NH N\ v 11 S0311GHQ-CH2 HG CH2 CHaCO CHx-QOJIH N\ CHr-CH:

CH3 01H Gian-0303K CH3.CO.CH:.CO.NH N\ 4 graphic silver halide gelatinemulsion containing amino group contain at least 9 carbon atoms.

3. A silver halide gelatin emulsion for color forming developmentcontaining an acylacetic acid arylide, said acyl radical being selectedfrom the class consisting of acyl radicals of the aliphatic and aromaticseries, said arylide containing at'least one water-solubilizing groupand said arylide having at least one amino group linked-to the ringsystem attached .to the amide nitrogen atom of said arylide, said aminogroup being selected from the class consisting of R --NR ma N/ in whichR selected from the class consisting of long-chain aliphatichydrocarbon, hydroaromatic, and aliphatic hydroaromatic radicals and R1is an aliphatic hydrocarbon radical, said water-solubilizing group beingattached to a carbon atom selected from the class consisting of anuclear carbon atom of s'aid ring system and a carbon atom of said longchain aliphatic hydrocarbon radical. 1

4, The composition as defined in claim 3 wherein said acylacetic arylideis anacetyl acetic acid arylide.

5. The composition as defined in claim 3 wherein said acylacetic acidarylide is an acetyl acetic acid arylide and in which the substituentson the nitrogen atom of said amino group contain at least 9 carbonatoms.

6. In a process of producing color photographic an acylacetic acidarylide, said acyl radical'being selected from the class consisting oiacyl radicals of the aliphatic and aromatic series, said arylidecontaining at least one water solubilizin oup and said arylide having atleast one amino group linked to the ring system attached to the amidenitro en atom of said arylide, said amino group being selected from thegroup consisting of NR and 'hydroaromatic and aliphatic hydroaromaticredprovement which comprises developing with an.

aromatic primary amino developer, an exposed silver halide emulsioncontaining a compound of the following formula:

I a-i-[E-i-om-i-Yl wherein A isan aromatic radical,

X is a water-solubilizing group,

Y is an acyl radical selected from the class consisting of acyl radicalsof the aliphatic and aromatic series,

B is an amino group linked to a nuclear carbon atom of said aromaticradical, said amino group being selected from the class consisting ofwherein R is a member of the class consisting of long-. chainaliphatichydrocarbon, hydroaromatic, and aliphatic-hydroaromatic radicals, and

R1 is an aliphatic hydrocarbon radical, and

n is a member of the group consisting or 1 and 2.

7. The process as defined in claim 6 wherein A isphenylandnislandxisasulfonicacid group.

8. A silver halide gelatin emulsion for colorforming developmentcontaining as a color former a compound of the following formula whereinchain aliphatic hydrocarbon, h droaromatic,

and aliphatlc-hydroaromatic r cals, and 7 R1 is an aliphatic hydrocarbonradical, and n is a member of the group consisting of 1 and 2,

9. A silver halide emulsion as defined in claim 8 wherein'A is phenyl, nis 1 andX-is a sulfonic acid'group. P p

10. A silver halide gelatin emulsionior colorforming developmentcontaining l-acetoacetylf amino-i-methyl-octadecylaminobenzene 3sulfonic acid;

, ,11. A silver halide gelatin emulsion for colorforming developmentcontaining l-acetoacetylamino-'i-methyl-ocadcylamino naphthalene-3sulfonicacid.

12. A silver halide gelatin emulsion for colorforming developmentcontaining ,l-aceto'a etylamino 2-inethy1 octadecy'lamino benzene--sulfohic acid. a I

' ALFRED r'abmm'cn.

wnmm'scmmm.

R is'a memberof the class consisting of long

